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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
NASA NTRS2016

Interfacial Structure and Capacitance of Li-doped Ionic Liquid Electrolytes from Molecular Simulations

Ionic liquids have been proposed as candidate electrolytes for high-energy density, rechargeable batteries, supercapacitors, and hybrid energy storage devices. Though Li-salt is often present in these systems, its influence on interfacial properties is largely uncharacterized. We, thereby, present an extensive computational analysis, supported by experimental comparisons, of the properties of a representative set of these electrolytesat an ideal carbon interface as a function of Li-salt doping and voltage. We have performed polarizable molecular (MD) dynamics simulations, using the APPLEP force field, to evaluate electric double layer (EDL) capacitance and distribution of Li+ in the EDL. Differential capacitance exhibits the characteristic camel profile and is insensitive to Li-doping. Li+ localizes in the second molecular layer of the EDL, which is a result of confinement from free energy barriers associated with ion layering. Joint MDelectronic structure computations show the electrochemical window of the electrolytes to be a weak function of Li-doping. Estimates of supercapacitor specific energy are made using the computed window and capacitance. The magnitude and trends in specific energy are in good agreement with experiment.

batteries↗
DOE OSTI2020

Accelerated Modeling of Lithium Diffusion in Solid State Electrolytes using Artificial Neural Networks

Abstract Previous efforts to understand structure‐function relationships in high ionic conductivity materials for solid state batteries have predominantly relied on density functional theory (DFT‐) based ab initio molecular dynamics (MD). Such simulations, however, are computationally demanding and cannot be reasonably applied to large systems containing more than a hundred atoms. Here, an artificial neural network (ANN) is trained to accelerate the calculation of high accuracy atomic forces and energies used during such MD simulations. After carefully training a robust ANN for four and five element systems, nearly identical lithium ion diffusivities are obtained for Li 10 GeP 2 S 12 (LGPS) when benchmarking the ANN‐MD results with DFT‐MD. Applying the ANN‐MD approach, the effect of chlorine doping on the lithium diffusivity is calculated in an LGPS‐like structure and it is found that a dopant concentration of 1.3% maximizes ionic conductivity. The optimal concentration balances the competing consequences of effective atomic radii and dielectric constants on lithium diffusion and agrees with the experimental composition. Performing simulations at the resolution necessary to model experimentally relevant and optimal concentrations would be infeasible with traditional DFT‐MD. Systems that require a large number of simulated atoms can be studied more efficiently while maintaining high accuracy with the proposed ANN‐MD framework.

Rao, Karun K.↗
DOE OSTI2020

Effects of surface charge and cluster size on the electrochemical dissolution of platinum nanoparticles using COMB3 and continuum electrolyte models

We study the site-dependent dissolution of platinum nanoparticles under electrochemical conditions to assess their thermodynamic stability as a function of shape and size using empirical molecular dynamics and electronic-structure models. The third-generation charge optimized many-body potential is employed to determine the validity of uniform spherical representations of the nanoparticles in predicting dissolution potentials (the Kelvin model). To understand the early stages of catalyst dissolution, implicit solvation techniques based on the self-consistent continuum solvation method are applied. It is demonstrated that interfacial charge and polarization can shift the dissolution energies by amounts on the order of 0.74 eV depending on the surface site and nanoparticle shape, leading to the unexpected preferential removal of platinum cations from highly coordinated sites in some cases.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Interfacial Atomistic Mechanisms of Lithium Metal Stripping and Plating in Solid–State Batteries

All-solid-state batteries based on a Li metal anode represent a promising next-generation energy storage system, but are currently limited by low current density and short cycle life. Further research to improve the Li metal anode is impeded by the lack of understanding in its failure mechanisms at lithium–solid interfaces, in particular, the fundamental atomistic processes responsible for interface failure. Here, using large-scale molecular dynamics simulations, the first atomistic modeling study of lithium stripping and plating on a solid electrolyte is performed by explicitly considering key fundamental atomistic processes and interface atomistic structures. In the simulations, the interface failure initiated with the formation of nano-sized pores, and how interface structures, lithium diffusion, adhesion energy, and applied pressure affect interface failure during Li cycling are observed. By systematically varying the parameters of solid-state lithium cells in the simulations, the parameter space of applied pressures and interfacial adhesion energies that inhibit interface failure during cycling are mapped to guide selection of solid-state cells. Furthermore, this study establishes the atomistic modeling for Li stripping and plating, and predicts optimal solid interfaces and new strategies for the future research and development of solid-state Li-metal batteries.

25 ENERGY STORAGE↗
DOE OSTI2020

Role of Solvent Rearrangement on Mg2+ Solvation Structures in Dimethoxyethane Solutions Using Multimodal NMR Analysis

One of the main impediments faced for predicting important emergent properties of a multivalent electrolyte (such as conductivity and electrochemical stability) is the lack of quantitative analysis of ion-ion and ion-solvent interactions, which manifest in solvation structures and dynamics. In particular, the role of ion-solvent interactions is still unclear in cases where the strong electric field from multivalent cations can influence structural evolution of lower permittivity organic solvent molecules on solvation structure. These influences are commonly refered to as electrostriction pheonmena. Using quantitative 1H, 19F, 17O, and 25Mg NMR together with 19F nuclear spin relaxation and diffusion measurments, we find an unusual correlation between ion concentration and solvation structure of Mg(TFSI)2 salt in dimethoxyethane (DME) solution. The domiant solvation structure evolves from contact ion pairs (i.e. [Mg(TFSI)(DME)1-2]+) to fully solvated clusters (i.e. [Mg(DME)3]2+) as salt concentration increases or as temperature decreases. This transition is coupled to a phase separation, which we study here between 0.06 M and 0.36 M. Subsequent analysis is based on an explanation of the electrostriction phenomena and the competion between solvent molecules and TFSI anions for cation coordination.

Chen, Ying↗
DOE OSTI2023

Understanding High-Voltage Behavior of Sodium-Ion Battery Cathode Materials Using Synchrotron X-ray and Neutron Techniques: A Review

Despite substantial research efforts in developing high-voltage sodium-ion batteries (SIBs) as high-energy-density alternatives to complement lithium-ion-based energy storage technologies, the lifetime of high-voltage SIBs is still associated with many fundamental scientific questions. In particular, the structure phase transition, oxygen loss, and cathode–electrolyte interphase (CEI) decay are intensely discussed in the field. Synchrotron X-ray and neutron scattering characterization techniques offer unique capabilities for investigating the complex structure and dynamics of high-voltage cathode behavior. In this review, to accelerate the development of stable high-voltage SIBs, we provide a comprehensive and thorough overview of the use of synchrotron X-ray and neutron scattering in studying SIB cathode materials with an emphasis on high-voltage layered transition metal oxide cathodes. We then discuss these characterizations in relation to polyanion-type cathodes, Prussian blue analogues, and organic cathode materials. Finally, future directions of these techniques in high-voltage SIB research are proposed, including CEI studies for polyanion-type cathodes and the extension of neutron scattering techniques, as well as the integration of morphology and phase characterizations.

25 ENERGY STORAGE↗
DOE OSTI2025

Modeling the Behavior of Complex Aqueous Electrolytes Using Machine Learning Interatomic Potentials: The Case of Sodium Sulfate

Understanding the structure and thermodynamics of solvated ions is essential for advancing applications in electrochemistry, water treatment, and energy storage. While ab initio molecular dynamics methods are highly accurate, they are limited by short accessible time and length scales whereas classical force fields struggle with accuracy. Herein, we explore the structure and thermodynamics of complex monovalent-divalent ion pairs using Na 2 SO 4 (aq) as a case study by applying a machine learning interatomic potential (MLIP) trained on density functional theory (DFT) data. Our MLIP-based approach reproduces key bulk properties such as density and radial distribution functions of water. We provide the hydration structure of the sodium and sulfate ions in the 0.1–2 M concentration range and the one-dimensional and two-dimensional potentials of mean force for the sodium–sulfate ion pairing at the low concentration limit (0.1 M), which are inaccessible to DFT. At low concentrations, the sulfate ion is strongly solvated, leading to the stabilization of solvent-separated ion pairs over contact ion pairs. Minimum energy pathway analysis revealed that coordinating two sodium ions with a sulfate ion is a multistep process whereby the sodium ions coordinate to the sulfate ion sequentially. Finally, we demonstrate that MLIPs allow the study of solvated ions beyond simple monovalent pairs with DFT-level accuracy in their low concentration limit (0.1 M) via statistically converged properties from ns-long simulations.

anions↗
DOE OSTI2025

Improving Ionic Conformality Across Polymer Electrolyte|Electrode Interfaces

Maintaining uniform ionic transport at electrode|electrolyte interfaces, i.e., ionic conformality, remains challenging in polymer electrolyte (PE)-based solid-state batteries. Morphological conformality does not necessarily imply ionic conformality. In PEs, which typically consist of a mechanically supporting component and distinct ionically conductive components, the rearrangement or depletion of mobile ion-conductive domains at interfaces can disrupt ionic transport pathways. Such localized ionic depletion contributes to interfacial instability and capacity degradation in high-voltage lithium-metal batteries. Herein, an electrolyte design approach aimed at minimizing interfacial heterogeneities is demonstrated through compositional adjustments, characterized by spatially resolved structural and chemical X-ray techniques and NMR diffusometry to elucidate ion transport dynamics. This approach improves ionic conformality at electrode interfaces, enhancing cycling stability in Li||LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NMC811) coin and pouch cells cycled at high voltages. These results contribute to understanding interfacial behaviors in multiphase PEs and inform strategies for improving stability across solid-state battery interfaces.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Innovative Symmetrical Electrolyte Architecture Enables Ultra-Flat and Thermal Resilient Protonic Ceramic Electrochemical Cells

Protonic ceramic electrochemical cells (PCECs) represent a promising class of solid‐state energy conversion devices capable of high‐efficiency hydrogen production and power generation. However, the practical deployment of planar PCECs is fundamentally constrained by severe structural deformation and mechanical failure during fabrication, stemming from asymmetric shrinkage between the thin electrolyte and the thick NiO‐based support layer. Here, in this work, a functionally integrated, symmetry‐engineered double‐sided electrolyte (DE) design is unveiled, which not only suppresses thermally induced curvature but also unlocks significant gains in electrochemical performance and stability. This architecture intrinsically balances shrinkage dynamics across the cell bilaterally, enabling the fabrication of ultra‐flat 5 × 5 cm 2 cells with sub‐100 µm thickness variation. A numerical solid mechanics simulation is introduced to investigate and interpret this achievement. Beyond structural advantages, the DE configuration enhances the cell operational stability, delivering a low open‐circuit voltage degradation of 9.5 mV/100 h across 80 thermal cycles. This work establishes a compelling paradigm wherein architectural symmetry directly translates to both mechanical fidelity and functional enhancement, offering a promising route toward PCECs scale‐up.

08 - HYDROGEN↗
DOE OSTI2021

Mechanistic Study of the Li–Air Battery with a Co 3 O 4 Cathode and Dimethyl Sulfoxide Electrolyte

The lithium–air battery, a powerful competitor to replace the traditional lithium-ion battery, has attracted increasing attention due to its extremely high theoretical energy density. However, its development is limited by the cathode and electrolyte properties, which should include high stability, conductivity, and electrocatalytic properties in oxygen-rich environments. Here, we employ a systematic first-principles study of Li–O 2 discharge and charge reactions on the Co 3 O 4 -based cathode with the assistance of dimethyl sulfoxide (DMSO) electrolyte. The structure, stability, and electronic properties of different surface reconstructions of the Co 3 O 4 (100) facet are investigated. In addition, the mechanisms and thermodynamic overpotentials of multi-step reactions between Li + /e – and O 2 are provided, where lithium suboxide products (Li 2 O 2 or Li 3 O 2 ) are formed on the different Co 3 O 4 (100) terminations. The solvation shell of Li + components in explicit DMSO solvent is investigated through ab initio molecular dynamics simulations. In general, we find that the Co 3 O 4 (100)-O (oxidized) surface is the most stable one under standard conditions, and the stable Li + solvation structure is found in a tetrahedral Li(DMSO) 4 + shell in the DMSO-based electrolyte. Moreover, in the system of the Co 3 O 4 (100)-O cathode and DMSO electrolyte, the solution model pathway is energetically favorable for the Li–O 2 discharge reaction. It provides a low constant overpotential of 0.17 V during a long-term discharging process, thus causing the final toroid Li 2 O 2 formation on the cathode. During the charging process, an overpotential of 0.36 V is required to rapidly decompose Li 2 O 2 .

25 ENERGY STORAGE↗
DOE OSTI2020

PDADMAC/PSS Oligoelectrolyte Multilayers: Internal Structure and Hydration Properties at Early Growth Stages from Atomistic Simulations

We analyze the internal structure and hydration properties of poly(diallyl dimethyl ammonium chloride)/poly(styrene sulfonate sodium salt) oligoelectrolyte multilayers at early stages of their layer-by-layer growth process. Our study is based on large-scale molecular dynamics simulations with atomistic resolution that we presented recently [Sánchez et al., Soft Matter 2019, 15, 9437], in which we produced the first four deposition cycles of a multilayer obtained by alternate exposure of a flat silica substrate to aqueous electrolyte solutions of such polymers at 0.1M of NaCl. In contrast to any previous work, here we perform a local structural analysis that allows us to determine the dependence of the multilayer properties on the distance to the substrate. We prove that the large accumulation of water and ions next to the substrate observed in previous overall measurements actually decreases the degree of intrinsic charge compensation, but this remains as the main mechanism within the interface region. We show that the range of influence of the substrate reaches approximately 3 nm, whereas the structure of the outer region is rather independent from the position. This detailed characterization is essential for the development of accurate mesoscale models able to reach length and time scales of technological interest.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Dynamical Ion Correlations in Polymer and Membrane Electrolytes: Recent Advances and Open Questions

Ion transport in polymer and membrane electrolytes is often described using uncorrelated models like the Nernst–Einstein (NE) approximation, which link conductivity, transference number, and salt diffusivity to individual ion mobilities. However, growing evidence shows that dynamical ion correlations─arising from ion pairing, polymer-mediated coupling, confinement, and electrostatic interactions─can substantially alter macroscopic transport properties. The Onsager transport formalism offers a rigorous framework to quantify these effects via cross-correlated ionic displacements. This Perspective highlights how such correlations manifest across dry and hydrated systems, including salt-doped polymers, block copolymers, hydrogels, and ion-exchange membranes. Here, we examine key physical origins, the influence of salt chemistry and polymer structure, and open questions in measuring and controlling correlated motion. Embracing correlation-aware design enables new pathways to optimize conductivity, transference number, and selectivity─shifting the focus from individual ion mobility to engineered collective dynamics for next-generation electrolytes in energy storage and separations.

Charge transport↗
DOE OSTI2021

Dynamic and weak electric double layers in ultrathin nanopores

The unique properties of aqueous electrolytes in ultrathin nanopores have drawn a great deal of attention in a variety of applications, such as power generation, water desalination, and disease diagnosis. Inside the nanopore, at the interface, properties of ions differ from those predicted by the classical ionic layering models (e.g., Gouy–Chapman electric double layer) when the thickness of the nanopore approaches the size of a single atom (e.g., nanopores in a single-layer graphene membrane). Here, using extensive molecular dynamics simulations, the structure and dynamics of aqueous ions inside nanopores are studied for different thicknesses, diameters, and surface charge densities of carbon-based nanopores [ultrathin graphene and finite-thickness carbon nanotubes (CNTs)]. The ion concentration and diffusion coefficient in ultrathin nanopores show no indication of the formation of a Stern layer (an immobile counter-ionic layer) as the counter-ions and nanopore atoms are weakly correlated in time compared to the strong correlation observed in thick nanopores. The weak correlation observed in ultrathin nanopores is indicative of a weak adsorption of counter-ions onto the surface compared to that of thick pores. The vanishing counter-ion adsorption (ion–wall correlation) in ultrathin nanopores leads to several orders of magnitude shorter ionic residence times (picoseconds) compared to the residence times in thick CNTs (seconds). The results of this study will help better understand the structure and dynamics of aqueous ions in ultrathin nanopores.

2D materials↗
DOE OSTI2024

The Challenge of Characterizing High-Concentration Electrolytes at the Molecular Level: A Perspective

High-concentration electrolytes (HCEs) are promising materials composed of highly concentrated salt solutions in organic solvents. HCEs have many desirable properties and are particularly important in the field of batteries. However, the number of ways in which these materials can be tuned is very large, which is crucial for tailored electrolyte design. Moreover, the molecular characterization of HCEs is challenging both experimentally and computationally, but it is necessary for their rational design. Therefore, currently the structure–property–performance relationship of these electrolytes has not been directly derived from their characterization. Here, in this Perspective, we present a brief overview of the HCEs and discuss the state-of-the-art characterization methods used to study them at the molecular level. We also address the challenges associated with these methods, including both experimental techniques and computational tools currently available. Emphasis is placed on methods aimed at understanding the physical phenomena that govern the molecular structure and dynamics occurring on the subnanosecond and nanometer time and length scales. Finally, we discuss new strategies for obtaining a comprehensive characterization of HCEs at the molecular level.

electrolytes↗
DOE OSTI2022

Operando X-ray Reflectivity Reveals the Dynamical Response of Ti 3 C 2 MXene Film Structure during Electrochemical Cycling

The dynamical structural response of MXenes during electrochemical ion intercalation is critical for their functionality in fast chemical actuation and high-power electrical energy storage but has yet to be observed. Here, the dynamically evolving layer spacing of a Ti 3 C 2 T $x$ MXene film was observed using time-resolved operando X-ray reflectivity during cyclic voltammetry for applied potentials between +0.3 and -0.7 V (vs Ag/AgCl) at sweep rates 1 ≤ $v$ ≤ 500 mV/s. The pseudocapacitive electrochemical MXene response in the aqueous 0.1 M Li 2 SO 4 electrolyte, including both capacitive and redox characteristics, is characterized by kinetically limited lithium intercalation and layer contraction. In conclusion, two types of dynamical responses were observed: slow and fast lattice contraction regimes versus applied potential are correlated with the capacitive and redox features, respectively, with structural relaxation rates that scale as ~$v$ 1/2 and ~$v$, revealing two distinct dynamical structural responses during electrochemical ion intercalation.

25 ENERGY STORAGE↗
DOE OSTI2021

Liquid state properties of SEI components in dimethoxyethane

The solid-electrolyte interphase (SEI) layer is a critical constituent of battery technology, which incorporates the use of lithium metals. Since the formation of the SEI is difficult to avoid, the engineering and harnessing of the SEI are absolutely critical to advancing energy storage. One problem is that much fundamental information about SEI properties is lacking due to the difficulty in probing a chemically complex interfacial system. One such property that is currently unknown is the dissolution of the SEI. This process can have significant effects on the stability of the SEI, which is critical to battery performance but is difficult to probe experimentally. Here, we report the use of ab initio computational chemistry simulations to probe the solution state properties of SEI components LiF, Li 2 O, LiOH, and Li 2 CO 3 in order to study their dissolution and other solution-based characteristics. Ab initio molecular dynamics was used to study the solvation structures of the SEI with a combination of radial distribution functions, discrete solvation structure maps, and vibrational density of states, which allows for the determination of free energies. From the change in free energy of dissolution, we determined that LiOH is the most likely component to dissolve in the electrolyte followed by LiF, Li 2 CO 3 , and Li 2 O although none were favored thermodynamically. Furthermore, this indicates that dissolution is not probable, but Li 2 O would make the most stable SEI with regard to dissolution in the electrolyte.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Understanding extreme fast charge limitations in carbonate mixtures

Charging large format lithium ion batteries within ten to fifteen minutes requires changes to the electrolyte composition in addition to modification of electrode and cell architectures. Several approaches to address this need have been proposed; but there is not a lot of clarity on understanding which factors limit the performance of existing electrolytes. Furthermore, this work takes a closer look at the solvated components of a mixture of LiPF 6 in ethylene carbonate (EC) and ethyl methyl carbonate (EMC) in the context of extreme fast charging and relates these findings to cell-level requirements. Molecular dynamics studies of the Gen-2 electrolyte compositions with increasing salt concentrations, have been performed to estimate transport properties like diffusivity, transference number and conductivity. Molecular-level differences in the structure of solvation shells under extreme LiPF 6 concentrations are probed here and some key aspects on solvent structure that help overcome barriers to Li + transport under extreme fast charge are discussed.

25 ENERGY STORAGE↗
DOE OSTI2022

An Investigation of Chemo-Mechanical Phenomena and Li Metal Penetration in All-Solid-State Lithium Metal Batteries Using In Situ Optical Curvature Measurements

Solid-electrolytes (SEs) can provide a pathway to increase energy-density in lithium metal batteries. However, lithium metal penetration through garnet based LLZO solid electrolytes has been identified as a critical failure process. This phenomenon is related to chemo-mechanical processes which are difficult to probe. In particular, characterizing the dynamic mechanical deformations that occur in electrode-SE structures is very challenging. Here study reports in situ curvature measurements that are thus designed to probe chemo-mechanical phenomena that occur during lithium plating. The novel experimental cell configuration created for this work shows that pressure builds up in the Li metal during plating, up until the point where short circuits occur. The resulting data are analyzed with a detailed finite element model (FEM) to quantitatively evaluate stress evolution. The results show that Li metal plating within a surface flaw can produce stress build-up prior to short-circuiting. The combined results from both the experiments and the FEM suggest that it is critical to minimize surface defects and flaws during the manufacturing processes.

25 ENERGY STORAGE↗